DE69708855T2 - HAIR COSMETIC COMPOSITION - Google Patents

Description

Technical area

The invention relates to a hair treatment composition which provides hair with improved natural shine or luster and enhanced manageability and can prevent hair damage and repair damaged hair.

State of the art

Hair cosmetic compositions must have properties such that they impart good gloss or sheen to hair and have enhanced styling ability. In order to obtain hair gloss, it has therefore been proposed to use a hair styling composition containing an oily substance or a polymer to coat the hair, thereby enhancing the reflection of light. For example, EP-A-688557 describes an aqueous hair spray composition comprising (i) a water-soluble polymer having a solution viscosity at 10% in water of less than about 20,000 cps at 25°C, the polymer being present in an amount effective to set the hair; and (ii) a latex of water-insoluble polymer particles dispersed in water, the average particle size of which is not greater than about 3 µm, the particles having a glass transition temperature of 250 to 300ºK and being present in an amount effective to interact with the polymer to further improve hair setting. Japanese Patent Laid-Open Publication No. 184115/1984 describes a hair cosmetic composition comprising 0.1 to 20 wt% of spherical particles of a water-insoluble polymer and 0.1 to 15 wt% of a cationic compound. Japanese Patent Laid-Open No. 310533/1993 describes a hair cosmetic composition comprising a powder of a cured polyorganosiloxane.

However, according to these methods, the intensity of the reflected light in fully coated areas of the hair becomes several times higher than that of the original hair, giving an unnatural appearance. In some cases, the composition adheres incompletely and strongly to the hair, resulting in low reflection of light. In any case, the sheen of the coated hair differs from the original hair in quality and feel, and the appearance becomes unnatural. In addition, the hairs stick together due to the film of the oily substance and the polymer, giving a dirty appearance.

On the other hand, in order to enhance the styling ability, it has been proposed to incorporate an oily substance or silicone into a shampoo, a hair conditioner, a hair treatment composition or a hair styling composition to cause such a component to be adsorbed onto the hair. However, this method also involves a problem in that the composition gives users an unpleasant feeling such as a sticky feeling of the whole hair.

Accordingly, it is an object of the invention to provide a hair cosmetic composition that imparts to hair an excellent natural shine or luster and improved styling ability.

In view of the above circumstances, the inventor has conducted an extensive investigation with the aim of solving the above problems.

Each hair fiber is coated with a layer of scaly cells called cuticle, which overlap each other in the form of a plate. Human hair is generally coated with 5 to 10 cuticle layers. A portion of the outermost layer is exposed to the environment. Of the exposed portion, the outer periphery of the cuticle cell is at an angle almost perpendicular to the axis of the hair. This portion will hereinafter be referred to as the marginal portion. Portions other than the outer periphery are at a shallow angle of about 5º with respect to the axis of the hair. These portions will hereinafter be referred to as the flat portion of the cuticle. This flat portion of the cuticle occupies most of the exposed area.

The inventor has thus found that when hair is treated with a composition containing fine particles of a water-insoluble polymer or inorganic material having an average particle diameter substantially equal to the height (0.2-1 µm) of the edge portion, the fine particles hardly adsorb on the flat portion of the cuticle and selectively adsorb on the edge portion. It has also been found that when the fine particles are selectively adsorbed on the edge portion, the steep angle of the edge portion is alleviated, improving the smoothness of the hair fibers, thereby imparting a good luster or luster to the hair. It has further been found that when the fine particles are caused to be adsorbed only on the edge portion while the flat portion of the cuticle, which accounts for the majority of the area of the hair surface, is adsorbed without coating the entire hair with the oily substance or polymer as in conventional hair styling compositions remains intact, thereby softening the angle of the edge part, allowing the hair to be given a natural shine or shimmer without increasing the intensity of the reflected light to an unnatural level when the hair is exposed to light.

According to the invention, there is thus provided a hair cosmetic composition comprising fine particles of a water-insoluble polymer or inorganic material having an average particle diameter of not smaller than 0.2 µm but smaller than 1 µm.

According to the invention there is also provided a method for making hair shiny and lustrous, comprising applying fine particles of a water-insoluble polymer or inorganic material having an average particle diameter of not smaller than 0.2 µm but smaller than 1 µm to the hair.

Short description of the drawings

Fig. 1 is an electron micrograph showing the inventive product 9 adsorbed on the hair.

Figure 2 is an electron micrograph showing the inventive product 10 adsorbed on the hair.

Fig. 3 is an electron micrograph showing the comparative product 6 adsorbed on hair.

Fig. 4 is an electron micrograph showing the comparative product 7 adsorbed on hair.

The fine particles useful in the practice of the present invention must have an average particle diameter of not smaller than 0.2 µm but smaller than 1 µm, preferably 0.3 to 0.9 µm. If the average particle diameter is smaller than 0.2 µm, the effects of imparting gloss or luster and improving the smoothness of hair cannot be sufficiently achieved. On the other hand, if the average particle diameter is not smaller than 1 µm, the number of fine particles adsorbed on the hair decreases so that the smoothness cannot be improved, resulting in a hair cosmetic composition incapable of imparting satisfactory gloss or luster. With respect to the particle size distribution of these fine particles, it is preferred that at least 80% of the fine particles be within a range of the average particle diameter of ± 30% in view of the effect of imparting good gloss or luster.

The average particle diameter and particle size distribution can be determined using a scanning electron microscope in the following manner.

A suspension of fine particles to be measured is applied to scanning electron microscopy slides to prepare samples such that the microscope can count several tens of particles in a field of view of 10,000x magnification. 10 micrographs of the sample are taken at different fields of view to determine the mean particle diameter, defined by the following equation, by means of an image analyzer.

where ni is the number of particles with a particle diameter of di.

There is no particular limitation on the shape of the fine particles; they may be in any shape, e.g., spherical, amorphous, flat or tabular, etc. They may also have any structure such as hollow and porous structure and the like. The fine particles may be subjected to surface modification, chemical treatment for imparting porosity, oil absorption ability or water absorption ability before use.

Of the fine particles used in the present invention, examples of the fine particles of the water-insoluble polymer include fine particles of polymers such as silicone resins, polymers of alkyl acrylates and copolymers with polymerizable monomers copolymerizable therewith, polymers of alkyl methacrylates and copolymers with polymerizable monomers copolymerizable therewith, polymers of styrene and copolymers of polymerizable monomers copolymerizable therewith, and chitosan-methacrylic acid copolymers.

Of these, water-insoluble silicone resins having a three-dimensionally cross-linked structure by siloxane bonding can be used as silicone resins. Commercially available products, e.g., Tospearl® manufactured by Toshiba Silicone Co., Ltd., KMP590 manufactured by Shin-Etsu Chemical Co., Ltd., and Trefil® R manufactured by Dow Corning Toray Silicone Co., Ltd. can be used.

The alkyl methacrylates with which the corresponding alkyl methacrylate polymers are formed include methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, n-hexyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate and n-lauryl methacrylate. Similarly, the alkyl acrylates with which the corresponding alkyl acrylate polymers are formed include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, n-hexyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate and n-lauryl acrylate.

Preferred alkyl methacrylate polymers are polymethyl methacrylate and polyethyl methacrylate, with polymethyl methacrylate being particularly preferred. Preferred alkyl acrylate polymers are polymethyl acrylate and polyethyl acrylate.

An example of a polymer copolymerizable with the alkyl acrylate or alkyl methacrylate is styrene. Examples of preferred copolymers thereof include styrene-butyl methacrylate copolymers. Examples of monomers copolymerizable with styrene include divinylbenzene and the like. Preferred copolymers of styrene include styrene-divinylbenzene copolymers.

Examples of the fine particles of the inorganic material include fine particles of titanium oxide, silica, aluminum oxide, iron oxide, zinc oxide, chromium oxide and mica.

The fine particles used in the present invention may or may not be charged with a positive or negative charge like the uncharged fine particles described above, but may be charged with a positive or negative charge. An example of negatively charged fine particles, in other words anionic fine particles, includes MP-1000 manufactured by Soken Chemical & Engineering Co., Ltd., which are fine particles of negatively charged polymethyl methacrylate. Fine particles of water-insoluble cationic polymers include fine particles of polymers having a cationic group such as a primary, secondary or tertiary amino group, or a quaternary ammonium group on at least a part of the main chains or side chains. Specific examples thereof include acrylic resin-amine adducts.

According to the invention, fine particles of a water-insoluble polymer or inorganic material which has been subjected to a surface treatment with a cationic, anionic and/or amphoteric compound can also be used.

Examples of the cationic compound used in surface treatment include cationic surfactants and cationic polymers.

The cationic surfactants include, for example, quaternary ammonium salts represented by the following general formulas (1) and (2):

wherein at least one of R¹, R², R³ and R⁴ is an alkyl or alkenyl group having a total of 8 to 28 carbon atoms, which may be substituted by an alkoxy, alkenyloxy, alkanoylamino or alkenoylamino group, wherein the remainder independently represents a benzyl group or a alkyl or hydroxyalkyl group having 1 to 5 carbon atoms, and X⊃min; is a halide ion or organic anion.

wherein at least one of R¹ and R² represents an alkyl or alkenyl group having a total of 8 to 28 carbon atoms, which may be substituted by an alkoxy, alkenyloxy, alkanoylamino or alkenoylamino group, the other being a benzyl group or an alkyl or hydroxyalkyl group having 1 to 5 carbon atoms, R⁵ and R⁶ independently represent an alkylene group having 2 to 3 carbon atoms, X- represents a halide ion or an organic anion, and r is an integer of 1 to 20.

Specific examples of X- which is a counter ion to each of the quaternary ammonium salts represented by the general formulas (1) and (2) include halide ions such as chloride, iodide and bromide ions; and organic anions such as methosulfates, ethosulfates, methophosphates and ethophosphates.

The cationic polymers include, for example, cationized cellulose derivatives, cationized starch, cationized guar gum derivatives, quaternary diallylammonium salt/acrylamide copolymers, quaternary poly(vinylpyrrolidone) derivatives, polyglycol-polyamine condensates.

Specific examples thereof include poly(dimethyldiallylammonium halide) type cationic polymers, represented by the following general formulas (3) or (4):

wherein R⁷ and R⁸ independently represent a hydrogen atom or a methyl group, X is a halogen atom and a is a number from 150 to 6,200; dimethylallylammonium halide-acrylamide copolymer type cationic polymers represented by the following general formula (5) or (6):

wherein R⁹ and R¹⁰ independently represent a hydrogen atom or a methyl group, X is a halogen atom or an organic anion, b + c is a number from 150 to 9,000; quaternary nitrogen-containing cellulose ethers; condensation products of tallow amine obtained from polyethylene glycol, epichlorohydrin, propylene amine and beef tallow fatty acid; condensation products of cocoylamine obtained from polyethylene glycol, epichlorohydrin, propylene amine and coconut oil fatty acid; and cationized products of vinylpyrrolidone-dimethylaminoethyl methacrylate copolymers.

Examples of the anionic compound include anionic surfactants and anionic polymers conventionally used in classical hair cosmetic compositions, etc. No particular limitation is imposed on the anionic surfactants used here as long as they are normally used in classical shampoo compositions, etc. Examples thereof include the following anionic surfactants (i) to (xi):

(i) straight-chain or branched alkylbenzenesulfonates having an alkyl group with an average of 10 to 16 carbon atoms;

(ii) alkyl or alkenyl ether sulfates containing an alkyl or alkenyl group having an average of 10 to 20 carbon atoms, to which ethylene oxide, propylene oxide, butylene oxide, or ethylene oxide and propylene oxide in a ratio of 0.1/9.9 to 9.9/0.1, or ethylene oxide and butylene oxide in a ratio of 0.1/9.9 to 9.9/0.1, are added in a ratio of an average of 0.5 to 8 moles per molecule;

(iii) alkyl or alkenyl sulfates containing an alkyl or alkenyl group with an average of 10 to 20 carbon atoms;

(iv) olefin sulfonates with an average of 10 to 20 carbon atoms per molecule;

(v) alkanesulfonates with an average of 10 to 20 carbon atoms per molecule;

(vi) saturated or unsaturated fatty acid salts containing an average of 10 to 24 carbon atoms per molecule;

(vii) Amidoethercarboxylic acid type surfactants represented by the following formula (7):

R¹¹-(OC₃H₆)d-(OC₂H₄)e-OCH₂-COOA (7)

wherein R¹¹ is a straight-chain or branched alkyl or alkenyl group having 8 to 22 carbon atoms, C₈₋₉-alkylphenyl or R¹²CONH-CH₂-CH₂-, wherein R¹² is a straight-chain or branched alkyl or alkenyl group having 11 to 21 carbon atoms, d is a number from 2 to 24, e is a number from 0 to 6, and A is a hydrogen atom, sodium, potassium, lithium, magnesium, a monoethanolamine residue, ammonium or a triethanolamine residue;

(viii) α-sulfofatty acid salts or esters containing an alkyl or α-alkenyl group having an average of 10 to 20 carbon atoms;

(ix) N-acylamino acid type surfactants having an acyl group with 8 to 24 carbon atoms and a free carboxylic acid residue;

(x) surfactants of the mono- or diphosphate type containing an alkyl or alkenyl group having 8 to 24 carbon atoms; and

(xi) Sulfosuccinates of higher alcohols having 8 to 22 carbon atoms, ethoxylates thereof or the like, or sulfosuccinates derived from higher fatty acid amides.

Examples of counterions to the anionic moieties of these anionic surfactants include ions of alkali metals such as sodium and potassium, ions of alkaline earth metals such as calcium and magnesium, an ammonium ion, and alkanolamines (e.g. monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, etc.) having 1 to 3 alkanol groups with 2 or 3 carbon atoms.

As anionic polymers, alkyl vinyl ether-maleic acid copolymers are preferred, with methyl vinyl ether-maleic acid copolymers being particularly preferred. This polymer is obtained by hydrolysis of a copolymer of benzyl ether with maleic anhydride and is commercially available under the trade names Gantrez® AN or Es. The copolymers may be partially esterified, e.g. by an ethyl, butyl or isobutyl residue (e.g. Gantrez® ES225). Other examples of the anionic polymers include vinyl acetate-crotonic acid copolymers and vinyl acetate-vinyl neododecanoate-croton terpolymers (known as Resin® series); sodium acrylate-vinyl alcohol copolymers (known as Hydagen® F); sodium polystyrene sulfonate (known as Flexane® 130); Ethyl acrylate-acrylic acid-N-tert-butylacrylamide terpolymers (known as Ultrahold®); vinylpyrrolidone-vinyl acetate-itaconic acid terpolymers; and acrylic acid-acrylamide copolymers and their sodium salts (known as Reten®).

Examples of the amphoteric compound include amphoteric surfactants and amphoteric polymers used in classical hair cosmetic compositions. The amphoteric surfactants include carbobetaine-type surfactants and sulfobetaine-type surfactants. The amphoteric polymers include, for example, N-octylacrylamide-(meth)acrylic acid-tert-butylaminoethyl methacrylate tert- polymers (known as Amphomer®); methacryloyloxyethyl betaine-alkyl methacrylate copolymer (known as Yukaformer®), in particular methacryloyloxyethyl betaine-butyl methacrylate copolymers (known as Yukaformer® Am75); Copolymers of monomers with a carboxylic acid or sulfonic acid, in particular copolymers of (meth)acrylic acid and/or itaconic acid with an amino group-containing monomer such as mono- or dialkylaminoalkyl(meth)acrylate or dialkylaminoalkyl(meth)acrylamide; copolymers of N-octylacrylamide, methyl methacrylate, hydroxypropyl methacrylate, N-tert-butylaminoethyl methacrylate and acrylic acid; and the copolymers described in US-3,927,199.

The surface treatment with any of these cationic, anionic or amphoteric compounds can preferably be carried out by using the fine particles and the ionic compound in a weight ratio of 1/20 to 20/1.

The hair cosmetic composition of the present invention may further contain a cationic, anionic or amphoteric compound in addition to the fine particles. Examples of such cationic, anionic and amphoteric compounds include the same compounds as those used in the surface treatment of the fine particles.

Preferred fine particles useful in the practice of the present invention include fine particles of a water-insoluble polymer selected from the group consisting of the above-mentioned silicone resins, polymers of alkyl acrylates and copolymers with polymerizable monomers copolymerizable therewith, polymers of alkyl methacrylates and copolymers with polymerizable monomers copolymerizable therewith, polymers of styrene and copolymers with polymerizable monomers copolymerizable therewith, and chitosan-methacrylic acid copolymers; and fine particles of an inorganic material selected from the group consisting of the above-mentioned titanium oxide, silica, aluminum oxide, iron oxide, zinc oxide, chromium oxide and mica.

In view of the adsorption efficiency of the fine particles on the hair and the preferable effects of preventing a "squeaky" feeling and a tight or stiff feeling on the hair after being applied to the hair, more preferable fine particles used in the present invention include fine particles of the cationic polymers; and fine particles obtained by subjecting the fine particles of the water-insoluble polymers or inorganic materials as mentioned above to a surface treatment with a cationic compound. Furthermore, incorporation of cationic compounds into the hair cosmetic composition in addition to the fine particles of the water-insoluble polymers or inorganic materials as mentioned above can achieve an improvement in these properties.

There is no particular limitation on the amount of the fine particles to be incorporated into the hair cosmetic composition of the present invention. However, it is preferable to use the fine particles in an amount of 0.001 to 10% by weight in view of the effect of making the hair shiny or lustrous and the inhibitory effects of the squeaky feeling and firm or stiff feeling. It is more preferable to vary the amount of the fine particles according to the use of the hair cosmetic composition. In the case of a hair cosmetic composition of the type which is rinsed out with water after being applied to the hair, such as a hair rinse, a hair conditioner or a rinse shampoo, the fine particles are preferably incorporated in an amount of 0.01 to 10% by weight. On the other hand, in the case of a hair cosmetic composition of the type which is not rinsed out after being applied to the hair, such as a hair treatment composition or a hair spray composition, the fine particles are preferably incorporated in an amount of 0.001 to 0.1% by weight.

When the cationic compound, anionic compound and/or amphoteric compound are incorporated in addition to the fine particles, these ionic compounds are preferably incorporated in an amount of 0.001 to 20 wt%.

In the hair cosmetic composition of the present invention, other ingredients conventionally used in classical hair cosmetic compositions, e.g. oily components such as hydrocarbons, higher alcohols, esters and silicone oil; wetting agents such as glycerin, propylene glycol, 1,3-butylene glycol and polyethylene glycol; surfactants such as anionic surfactants, nonionic surfactants and amphoteric surfactants; medicinally effective agents such as antidandruff agents and vitamins; antiseptic agents such as parabens; thickening agents such as water-soluble polymers; coloring agents such as dyes and pigments; pearl-like tone-imparting agents such as glycol esters; and additionally chelating agents, various fragrances and the like suitable in addition to the above described components may be incorporated, provided that this does not adversely affect the effects according to the invention.

According to the hair cosmetic composition of the present invention, the water-insoluble fine particles incorporated therein can selectively adsorb on the peripheral part of the hair cuticle, thereby imparting a natural luster or luster to the hair, thereby giving the user a comfortable feeling without a sticky feeling and enhancing the styling ability. It is also possible to previously allow an oily substance to adsorb on the fine particles so as to cause the oily substance to adsorb only on the peripheral part of the cuticle which is easily damaged, thereby effectively exhibiting a repairing effect on the damaged hair.

The words "selective adsorption on the edge part" as used herein mean that the amount of the fine particles adsorbed on the edge part is at least 70% of the amount of the fine particles adsorbed on the entire hair cuticle. It is particularly preferable that the amount of selective adsorption is at least 80%. This amount of adsorption can be determined by observing the cuticle on which fine particles have been adsorbed by an electron microscope, counting the number of fine particles adsorbed on the edge part and the flat part of the cuticle.

According to the present invention, natural luster or luster is imparted to hair by adsorbing fine particles on the peripheral part of the hair cuticle. However, it is preferred that the fine particles adsorb on the peripheral part in a ratio of 5 particles or more, preferably 15 particles or more per unit surface area, 1,000 µm², of the hair and occupy at least 70%, preferably at least 80% of the adsorbed fine particles on the edge part. The amount of adsorbed fine particles per unit surface area of the hair can also be counted by observation through an electron microscope.

Examples

The invention will hereinafter be described in more detail by the following examples. However, the invention is not limited to these examples.

Example 1:

Hair rinse compositions having the respective formulations shown in Tables 1 to 4 were prepared according to a method known per se in the art to evaluate them for selective adsorption capacity on the edge part, gloss or luster enhancing effect and styling ability. The results are shown in Tables 1 to 4.

The hair of a subject was divided into two halves, and each of the hair rinse compositions containing fine particles according to the invention was applied to one half, while a hair rinse composition containing no fine particles (Comparative Product 1) was applied to the other half. The hair thus treated was rinsed and dried.

(1) Evaluation of the selective adsorption capacity on the edge part:

20 hairs were collected from the part of the subject's hair that had been treated with the rinse composition containing fine particles, and 10 micrographs per hair were taken at a magnification of 10,000, when the rinsing composition contained fine particles having an average particle diameter of less than 0.2 µm, at a magnification of 2 000 when the rinsing composition contained fine particles having an average particle diameter of not less than 0.2 but less than 1 µm, and at a magnification of 800 when the rinsing composition contained fine particles having an average particle diameter of not less than 1 µm.

The number of particles adsorbed on the edge part and on the entire hair cuticle was counted to determine the percentage of particles adsorbed on the edge part as an average value on the hair surface according to the following equation, thereby classifying the selective adsorption capacity on the edge part according to the following standard.

A: at least 70%; and

C: less than 70%.

(2) Evaluation of the amount of adsorbed particles:

The number of particles adsorbed on the hair per surface area of 1,000 µm² was counted by an electron microscope to determine the average value, whereby the amount of adsorbed particles was classified according to the following standard.

A: at least 5 particles per 1 000 um²; and

C: less than 5 parts per 1 000 µm².

(3) Evaluation of the shine and shimmer enhancing effect:

A panel of 10 people visually assessed the shine or shimmer enhancing effect on each subject, thereby making a rating according to the following standard.

AA: All jury members assessed that the inventive composition was effective in comparison with the hair conditioner composition without fine particles (Comparative Product 1);

A: 7 to 9 jury members assessed that the inventive composition was effective in comparison with the hair conditioner composition without fine particles (Comparative Product 1);

B: 4 to 6 jury members assessed that the inventive composition was effective in comparison with the hair conditioner composition without fine particles (Comparative Product 1); and

C: A maximum of 3 jury members assessed that the inventive composition was effective in comparison with the hair conditioner composition without fine particles (Comparative Product 1).

(4) Assessment of the effect of enhancing the hair-styling ability:

10 jury members visually assessed the effect of enhancing the hairdressing ability for each Subject, resulting in classification according to the following standard.

AA: All jury members assessed that the inventive composition was effective in comparison with the hair conditioner composition without fine particles (Comparative Product 1);

A: 7 to 9 jury members assessed that the inventive composition was effective in comparison with the hair conditioner composition without fine particles (Comparative Product 1);

B: 4 to 6 jury members assessed that the inventive composition was effective in comparison with the hair conditioner composition without fine particles (Comparative Product 1); and

C: A maximum of 3 jury members assessed that the composition according to the invention was effective in comparison with the hair conditioner composition without fine particles (Comparative Product 1). Table 1 Table 1 (continued)

*1: Idemitsu Titania IT-S (product of Idemitsu Kosan Co., Ltd.).

*2: Tospearl® 105 (product of Toshiba Silicone Co., Ltd.).

*3: Tospearl® 145A (product of Toshiba Silicone Co., Ltd.).

*4: MP-1451 (Product of Soken Chemical & Engineering Co., Ltd.).

*5: MP-1600 (Product of Soken Chemical & Engineering Co., Ltd.).

*6: MX-500 (Product of Soken Chemical & Engineering Co., Ltd.).

*7: MUTICLE® PP240D (product of Mitsui-Toatsu Chemicals, Inc.). Table 2 Table 2 (continued)

*1: Idemitsu Titania IT-S (product of Idemitsu Kosan Co., Ltd.).

*2: Tospearl® 105 (product of Toshiba Silicone Co., Ltd.).

*3: Tospearl® 145A (product of Toshiba Silicone Co., Ltd.).

*4: MP-1451 (Product of Soken Chemical & Engineering Co., Ltd.).

*5: MP-1600 (Product of Soken Chemical & Engineering Co., Ltd.).

*6: MX-500 (Product of Soken Chemical & Engineering Co., Ltd.).

*7: MUTICLE® PP240D (product of Mitsui-Toatsu Chemicals, Inc.). Table 3 Table 3 (continued)

*1: Idemitsu Titania IT-S (product of Idemitsu Kosan Co., Ltd.).

*2: Tospearl® 105 (product of Toshiba Silicone Co., Ltd.).

*3: Tospearl® 145A (product of Toshiba Silicone Co., Ltd.).

*4: MP-1451 (Product of Soken Chemical & Engineering Co., Ltd.).

*5: MP-1600 (Product of Soken Chemical & Engineering Co., Ltd.).

*6: MX-500 (Product of Soken Chemical & Engineering Co., Ltd.).

*7: MUTICLE® PP240D (product of Mitsui-Toatsu Chemicals, Inc.).

*8: Spherical TiO2 particles (product of Hokko Chemikal Industry Co., Ltd.).

*9: Fine particles of surface-treated black iron oxide (product of Titan Kogyo KK). Table 4 Table 4 (continued) Table 4 (continued)

*1: Idemitsu Titania IT-S (product of Idemitsu Kosan Co., Ltd.).

*2: Tospearl® 105 (product of Toshiba Silicone Co., Ltd.).

*3: Tospearl® 145A (product of Toshiba Silicone Co., Ltd.).

*4: MP-1451 (Product of Soken Chemical & Engineering Co., Ltd.).

*5: MP-1600 (Product of Soken Chemical & Engineering Co., Ltd.).

*6: MX-500 (Product of Soken Chemical & Engineering Co., Ltd.).

*7: MUTICLE® PP240D (product of Mitsui-Toatsu Chemicals, Inc.).

*8: Spherical TiO2 particles (product of Hokko Chemical Industry Co., Ltd.).

*9: Fine particles of surface-treated black iron oxide (product of Titan Kogyo K.K.).

*10: About 70% of the particles have an average particle diameter within ± 30%, and about 30% of the particles in the outer region have an average particle diameter of ± 30%.

Example 2:

Hair cosmetic compositions with the corresponding formulations shown in Table 5 were prepared according to a prepared by a method known in the art per se and sprayed separately onto a hair bundle. After air-drying the thus-treated hair bundles, the hair cosmetic compositions were evaluated for the selective adsorption capacity on the edge part in the same manner as in Example 1. In addition, the gloss or luster-enhancing effects were visually evaluated by 10 panel members. The results are shown in Table 5. Table 5

*5: MP-1600 (Product of Soken Chemical & Engineering Co., Ltd.).

*11: Polyquat® NH (product of Henkel Hakusui Corporation).

9 out of 10 jury members assessed that the hair bundles sprayed with the inventive product 9 and the inventive product 10 were superior to both the comparative product 6 and the comparative product 7 in terms of both intensity and the advantage in terms of shine.

Example 3:

A rinse composition was prepared according to the following formulation.

(% by weight)

(1) Hydroxyethylcellulose 1

(2) Polyoxypropylene polyoxyethylene alkyl ether phosphate 1

(3) Polyoxyethylene alkyl ether 3

(4) Polyoxyethylene hardened Castor oil 0.5

(5) Stearyltrimethylamminium chloride 1

(6) Liquid paraffin 0.5

(7) Propylene glycol 15

(8) Ethanol 5

(9) Sodium hydroxide 0.1

(10) Ion exchanged water 65.9

(11) Dispersion of cationized fine particles of polymethyl methacrylate*12 7.0

*12: Obtained by adding 10 g of fine polymethyl methacrylate particles*13 to 60 g of a 0.2% aqueous solution of stearyltrimethylammonium chloride and stirring the mixture into a dispersion.

*13: Fine particles of polymethyl methacrylate, MP-5000 (spherical; average particle diameter: 0.4 µm; product of Soken Chemical & Engineering Co., Ltd.)

After heating to 70°C the components (1), (3) to (7) and (10) and mixing, the mixture was cooled to 50°C, and the components (2), (8), (9) and (11) were added thereto. The resulting mixture was cooled with stirring.

Examples 4 and 5:

Rinse compositions were prepared according to the following respective formulations.

(12) Ion-exchanged

*14: Positively charged particles, MP-5500 (+450 uc/g; spherical; average particle diameter: 0.4 μm; product of Sokon Chemical & Engineering Co., Ltd.).

*15: Positively charged particles, MP-2701 (+500 uc/g; spherical; average particle diameter: 0.4 μm; product of Sokon Chemical & Engineering Co., Ltd.).

Example 6

A hair spray composition was prepared by mixing the following components.

(% by weight)

(1) Dispersion of cationized styrene-divinylbenzene-alkyl acrylate terpolymer*16 1.5

(2) Ethanol 5.0

(3) Fragrance q.s.

(4) Colorants q.s.

(5) Ion-exchanged water residue

Example 7

A hair spray composition was prepared by mixing the following components.

(% by weight)

(1) Aqueous dispersion of cationized TiO2 25

(2) Fragrance q.s.

(3) Colorants q.s.

(4) Aminoethylaminopropylsiloxane-dimethylsiloxane copolymer emulsion*19 0.25

(5) Ion-exchanged water residue

*18: Obtained by adding 0.02 g of TiO₂*20 to 50 g of a 0.3% solution of Celquat® L-200*19 and stirring the mixture into a dispersion.

*19: Product of National Starch Co.; Polyquaternium-4.

*20: Spherical TiO2 particles (average particle diameter: 0.6 µm; product of Hokko Chemical Industry Co., Ltd.).

*21: SM8702C (product of Dow Corning Toray Silicone Co., Ltd.).

Example 8

A hair spray composition was prepared by mixing the following components.

(% by weight)

(1) Aqueous dispersion of cationic TiO₂*22 25

(2) Fragrance q.s.

(3) Colorants q.s.

(4) Diethylene glycol monoethyl ether 20

(5) Ion-exchanged water residue

*22: Obtained by adding 0.12 g of TiO₂*20 to 100 g of a 3% aqueous solution of Gafquat® 734*23 and stirring the mixture in a dispersion.

*23: Product of ISP Co.; Polyguaternium-11.

Comparison example 8:

A rinse composition was prepared in the same manner as in Example 3 except that ion-exchanged water was added instead of component (11).

Comparison example 9:

A hair spray composition was prepared in the same manner as in Example 6 except that ion-exchanged water was added in place of component (1).

Comparison example 10:

A hair spray composition was prepared in the same manner as in Example 7 except that a 0.3% aqueous solution of Celquat® L-200 was used instead of component (1).

Comparison example 11:

A hair spray composition was prepared in the same manner as in Example 7 except that a 0.3% aqueous solution of Gafquat® 734 was used instead of component (1).

Test example:

Female test subjects separately used the hair cosmetic compositions obtained in Examples 3 to 8 and Comparative Examples 8 to 11, and 10 jury members visually evaluated the respective compositions for the gloss or luster enhancing effect and the effect of enhancing styling ability.

The evaluation was conducted by comparison between the compositions of Examples 3 to 5 and the composition of Comparative Example 8, between the composition of Example 6 and the composition of Comparative Example 9, between the composition of Example 7 and the composition of Comparative Example 10, and between the composition of Example 8 and the composition of Comparative Example 11, thereby classifying them into the following standards.

AA: All 10 jury members judged that the composition of the example was more effective than that of the comparison example;

A: 7 out of 9 jury members judged that the composition of the example was more effective than that of the comparison example;

B: 4 out of 6 jury members judged that the composition of the example was more effective than that of the comparison example;

C: A maximum of 3 jury members judged that the composition of the example was more effective than that of the comparison example. Table 6

According to the hair cosmetic compositions of the present invention, the water-insoluble fine particles incorporated therein are selectively adsorbed onto the peripheral part of the hair cuticle, thereby allowing the hair to be given a natural luster or luster, giving the user a comfortable feeling without a sticky feeling, and enhancing the styling ability.

The invention has been disclosed by way of general description and by way of specific examples.

Claims (13)

1. A hair cosmetic composition comprising fine particles of a water-insoluble polymer or inorganic material having an average particle diameter of not smaller than 0.2 µm but smaller than 1 µm. 2. The hair cosmetic composition according to claim 1, wherein the average particle diameter of the fine particles is 0.3 to 0.9 µm. 3. The hair cosmetic composition according to claim 1, wherein the particle size distribution of the fine particles is such that at least 80% of the fine particles are in a range of the average particle diameter of ±30%. 4. The hair cosmetic composition according to claim 1, wherein the fine particles selectively adsorb to the peripheral part of the hair cuticle. 5. The hair cosmetic composition according to claim 1, wherein the fine particles are those of a water-insoluble polymer selected from the group consisting of silicone resins, polymers of alkyl (meth)acrylates and copolymers thereof with monomers copolymerizable therewith, polymers of styrene and copolymers thereof with monomers copolymerizable therewith, and chitosan-methacrylic acid copolymers, or fine particles of an inorganic material selected from the group consisting of titanium oxide, silicon oxide, aluminum oxide, iron oxide, zinc oxide, chromium oxide and mica. 6. The hair cosmetic composition according to claim 1, wherein the fine particles are those of a water-insoluble cationic polymer. 7. The hair cosmetic composition according to claim 1, wherein the fine particles are fine particles surface-treated with a cationic compound. 8. Hair cosmetic composition according to claim 1, further comprising a cationic compound. 9. The hair cosmetic composition according to claim 1, wherein the fine particles are contained in an amount of 0.001 to 10 wt.%. 10. A hair cosmetic composition according to claim 1, wherein the fine particles are contained in an amount of 0.001 to 0.1% by weight and the composition is one which is not rinsed off with water after being applied to the hair. 11. A hair cosmetic composition according to claim 1, wherein the fine particles are contained in an amount of 0.01 to 10% by weight, and the composition is one which is rinsed off with water after being applied to the hair. 12. A method for making hair shiny and lustrous, comprising applying the hair cosmetic composition according to claim 1 to the hair. 13. A method for making hair shiny and lustrous, comprising applying fine particles of a water-insoluble polymer or an inorganic material having an average particle diameter of not smaller than 0.2 µm but smaller than 1 µm, to the hair.